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Patented 051. 11, 1932 UNITED STATES PATENT orrlce EUGEN GLIETENBEBG AND WILHELI mmmlm OI LEVEBKUBEN-OH-THE-Bm AND JOSEF KALLEB, OI WIESDOBF-ON-THE-BKINE, GERMANY, ABSIGNOBS TO GENERAL ANILINE WORKS, INC, OF NEW Yon-3.1T. Y. A CORPORATION OF DELL- WARE WATER SOLUBLE DIAzO-AIIHO COMPOUND No Drawing. Application filed April 85, 1929, Serial Io. 858,158, and in Germany April 30, 1888.

wherein R stands for the nucleus of an aro-' matic amine capable of producing azodyestuffs, which may be substituted by substituents of the group consisting of alkyl, alkoxy, halogen, the nitro group and a substituted amino group, and which may be connected with another aromatic nucleus by means of 5 an azo group, R and R stand either for the same or different residues of the group comprising alkyL, benzyl-, phenyland cyclohexyl-groups, at least one of which being substituted by a substituent inducing solubilit in water, such as the -COOH,-SO H or .sO H-groups, and n stands for one of the numbers one and two.

Our new compounds are obtainable by slowly introducing the solution of a diazo or tetrazo compound which has been prepared in the usual manner by diazotization of a primary aromatic amine or amino azo dyestu if of the kind referred to with hydrochloric or sulfuric acid and sodium nitrite into the solution of about equimolecular quantity or about double molecular quantity respectively of a secondary amine of the general formula wherein R and R 7 stand either for the same or different residues of the group comprising alkyl benzyl-, phenyland cyclohexylresidues, but at least one of the symbols R and R containing a substituent inducing solubility in water, such as the -COOH. -SO H and O.SO H groups, care being taken that an acid binding agent, such as magnesia, sodium acetate, a caustic alkali,

an alkali metal carbonate or bicarbonate, pyridine or the like is present for removing the free acid liberated in the condensation process. Such secondary amines of the general formula:

are, for example, to mention only a few of those known, sarcosine, diglycolamino acid, dibenzylamino disulfonic acid and methylamine-formaldehyde sulfurous acid. The process is generally carried out atlow temperature, say at about 0 C. to about 10 0.; the new condensation productseither separate during the reaction or are salted out 'with potassiumor sodium chloride, when the reaction is complete after a short time.

Our new compounds are obtained generally as colorless to yellowish colored crystals; 7

they are very stable both in the dry state and also in aqueous neutral or alkaline solution On the addition of a mineral acid, an acid mineral acid salt, such as sodium bisulfate, or a strong organic acid, such as acetic acid, formic acid and oxalic acid, they are split up into the two starting components, that means into a diazo or tetrazo compound and into one or two molecules of a secondary amine of the general formula R and R meaning the same as above de- I scribed.

Our new condensation products are valuable substances in' the manufacture of dyeand 690 ccm. of 1 sodium nitrite solution. The diazo solution is run slowly into a solution of 250 grams of the sodium salt of mono ethyl 2 toluidine 4 sulfonic acid (CH =1) cooled below 10 C. and containing as acid fixing agent 120 grams of potassium carbonate. The reaction is soon complete and the condensation product having in its free state the following formula:

CH: 503E CzHa N=N-N separates during the reaction as the potassium salt in a beautiful crystalline form.

Instead of potassium carbonate other acid fixing agents, such as sodium carbonate, bi-

carbonate, magnesia, caustic alkaliels and the like can be used.

- Emample 2.95 grams of sodium carbonate are added to a solution of 235 grams of the sodium salt of mono-ethyl-meta-sulfanilic acid in 500 ccm. of water, and at a temperature below 10 C. the diazo solution'obtained SOaH from 168 grams of 5-nitro-2-anisidine (OCH =1), 400 com. of water, 200 ccm..of 28% hydrochloric acid and 690ccm. of 10% sodium nitrite solution is slowly run in. The sodium salt of the reaction product is par tially precipitated. On the addition of sodium chloride a larger quantity thereof is obtained.

Example 3.'138 grams of meta-nitraniline are diazotized as described above, and'this solution is added slowly to a solution of 220 grams of sodium monomethylanilinel-sulfonate in, 500 ccm. of water cooled below 10 C. and containing 120 grams of potassium carbonate. The condensation product forms readily and separates in the form of the well crystallized potassium salt on salting out with potassium chloride.

-Emample 4. When the diazo solution obtained from one mol of l-amino-carbazole is run slowly into an alkaline sodium carbonate solution of 1.1 mols of sarcosine, the formation of the following diazo-amino compound having in its free state the following formula takes place very quickly. Its sodium salt can be separated completely by the addition of sodium chloride.

Example 5.157.5 grams of 4-chloro-2- anisidine are diazotized and introduced slowly into an alkaline sodium carbonate solution of 1.1 mols of monoethyl-p-toluidine sulfonic acid. The sodium salt of the condensation product Cl OCH:

(llzHs N=N- Qua.

OCH: OCH;

formed is separated by salting out,

Ewample 7.127.5 grams of 4-chloroaniline are diazotized in 400 ccm. of water and 200 com. of 28% hydrochloric acid with 690 ccm. of sodium nitrite solution, and this solution is added slowly to an aqueous solution of 300 grams'of the neutral sodium salt of the monoglycinated 4-sulfanilic acid rendered alkaline by means of' alkali carbonate. condensation product can be obtained in a The beautiful crystalline form on the addition of common salt.

Example 8.-The diazo solution obtained from 168 grams of 5.-nitro-2-anisidine is run slowly into an alkaline potassium carbonate solution of 1.1 mols of monoethyl-p-toluidine sulfonic acid, whereupon the condensation product partly separates. When the reaction is complete, the potassium salt of the condensation product of the following formula:

(IDCHa I 2H 803B is isolated completely by salting out with potassium chloride.

Eacample 9.When the diazo solution obtained from one molecule of 5-nitro-2-toluidine is caused to react with a solution (rendered alkaline with bicarbonate) of 1.1 mols of the condensation product obtained from equivalent parts of 4-toluidine and formaldehyde bisulfite, the resulting reaction product;

4 N0 dare-eon:

can be separated in the customary manner.

Example 10.138 grams of m-nitraniline are diazotized in the customary manner and coupled with 153 grams of ammohydroquinone dimethyl ether in hydrochloric acid solution. The suspension of the azo dyestufi, thus obtained is then converted into the diazoazo compound by treatment with 120 grams of concentrated hydrochloric acid and 69 grams of sodium nitrite, which is poured slowly with stirring into a solution of 100 grams of sarcosine containing an excess of sodium carbonate. When the reaction is complete, the condensation product is separated by the addition of sodium chloride; it is a brown powder, which dissolves in water with a ye lowish brown coloration. In its free state it possesses the following constitution:

OCH:

Ewample 11.-The diazo solution obtained from-141.5 grams of 4-chloro-2-toluidine, 200 ccm. of 28% hydrochloric acid, L00 ccm. of water and 690 ccm. of 10% sodium nitrite solution is run slowly at a temperature of below 10 G. into a solution of 100 grams of sarcosine in water with the addition of 185 grams of potassium carbonate. The coupling reaction is soon complete. The solution is evaporated to dr ess under reduced pressure, and the residue containing the potassium salt of the condensation product can be used without further treatment.

Instead of potassium carbonate, sodium carbonate, bicarbonate, caustic alkalies and the like, can be used as acid fixing agents.

Ea'ample 12.The diazo solution obtained from 141.5 grams of 4-chloro-2-toluidine, 200 ccm. of 28% hydrochloric acid, 400 com. of water and 690 com. of 10% sodium nitrite solution is slowly run into a solution of 146 grams of diglycolamino acid Gin-coon oin-coon in water with the addition of 256 grams of potassium carbonate. The reaction is soon complete. The condensation product CHa-COOH N=N-1-/ oin-ooon SOaH SOaH 3 can be separated in a crystalline form as the potassium salt.

Example 14-.-One mol of 5-nitro-2-toluidine is diazotized in hydrochloric acid solution, and this solution is added slowly in the cold to a solution (rendered alkaline with alkali carbonate) of 1.1 mols of the condensation product obtained from one mol of hexyhydroanr'line and one mol of chloro acetic acid. The condensation product separates already during the reaction as a potassium salt.

from one mol of ortho-anisidine is run slowly in the cold into an aqueous solution of 1.1 mols of N-methylbenzylamino sulfonic acid in the presence of potassium bicarbonate. The condensation product formed can be separated in the crystalline form as the potassium salt.

Example 16.-The formaldehyde bisulfite compound from one mol of formaldehyde and one mol of sodium bisulfite is stirred for half an hour at' (SO-70 C. with one mol of glycocol when condensation to the following substance occurs oin.ooon

\CH2.0.S02Na To the aqueous solution of this secondary amine is run in slowly in the presence of potassium carbonate the diazo solution obtained from 0.9 mol of 5-chloro-2-toluidine.-

Condensation is soon complete. The condensation product can be separated as the potassium salt on the addition of potassium chloride.

v Example 17.157 .5 grams of 4-chloro-2- Example 15.The diazo solution obtained anisidine are diazotized and introduced sl'owly into an alkaline sodium carbonate solution of 1.1 mols of sarcosine. The formation of the following diazo amino compound having in the free state the formula: 4

OCH:

an, tn;

takes place very quickly. The new compound can be separated completely by the addition of sodium chloride. I

We claim: 1. The compounds of the probable generalwherein R stands for the nucleus of an aromatic amine capable of producing aZ'odye:

stufi's which may be substituted bysubstituents of the group consisting of alkyl, alkoxy, halogen, the nitro group and a substituted amino group, R and R stand for substituents of the group consisting of alkyl-, ben zyl phenyland cyclohexyl-groups, at least one of which containing a substituent of the groupconsisting of the COOH, SO H and (LS'O H groups, and n stands for one of the numbers one and two, being generally colorless to yellowish colored crystals, being very' stable in their dry state and in aqueous and" alk'a line solution, and being valuable substances in the manufacture of dyestuffs and for combating insect'pests.

2. The compounds of the probable general formula:

R1 RN=NN/' wherein R stands for the nucleus of an arcmatic amine capable of producing azodye-' stuffs which may be substituted by substituents of the group consisting of alkyl, alkoxy, halogen, the ni'tro group and a substituted amino group, R and R stand for substitu; ents of the group consisting of alkyl-, benzyL,

phenyland cyclohexyl-groups, at least one .of which containing a substituent of the group consisting of the COOH, SOQH and yellowish colored or stals, being very stable in their dry state an in aqueous and alkaline O.SO H groups, beinggenerally colorless to": i

solution, and being. valuable substances in the manufacture ofdyestufl's and'for combating insect pests.

3. The compounds of the probable general formula-z wherein stands for the nucleus-off 9 A matic amine-"capable of producing a'zodye% stufis which may be- 'substltuted byj siibstitd,

ents ofth'e group consisting of alkyl, alkoiy,

halogen, the. nitrogroupand asubstituted a sessment 0: ylgrc'u which amino group, R stands; the group" consisting may be substituted-by.

. rb y acid} group, a penyle', a be 'yl sulfon ic acid, group and a cyclohexyl residue; andfR 'stands for a substituent of. the groupfconsisting of an alkyl sulfonic acid group,- an"alkyl carboxy lic acid group, a phenylsulfonic acid group and a benzylsulfon'ic acid group, being gem erally colorless'to yellowish' coloredcrystals, being very stable intheii', dry state and in aqueous and alkaline 'solution,'- and being valuable substances in the manufacture ofdyestuifsyand for combating insect pests.

4. The compounds of'the' probablegeneral wherein R stands for the nucleus" of an aromatic amine capable of producing a'zodyestuifs which may be substituted by substitucuts of the group consisting of alkyl,'alkoxy,

'h'alogen,.. the nitro group and a] substituted amino group,- R' stands for an akyl which is substituted by a carboxylic acidgroup, being generally colorless to yellowish colored crystals, being very stable in' their dry state and in 7 aqueous and alkaline solution, and being'valuable substances in the manufacture of dyestuffs and for combating insect pests.

5. The compounds of the probable general formula I,

wherein Rstands'for the nucleus of an arcmatic amine capable oft-producing azodyestuffs which may be substituted by substituents of the group consisting, of alkyl, al-

koxy, halogen, the nitro group and a substituted amino group, being generally color.- less to yellowish colored crystals, being very stable in their dry state and in aqueous and alkaline solution, and being valuable substances in the manufacture of dyestufi's and for combating insect pests.

6. The compounds of the probable general formula:

wherein It stands for a benzene nucleus which may be substituted by substituents of the group consisting of alkyl, alkoxy, halogen, the nitro group and a substituted amino group, R, and R stand for substituents of the group consisting of alkyl-, benzyh, phenyland cyclohexyl-groups, at least one of which'containing a substituent of the group consisting of the COOH, 30,11 and OSO H groups, being generally colorless to yellowish colored crystals, being very stable in their dry state and in aqueous and alkaline solution, and being valuable substances in the manufacture of dyestuffs and for cornbating insect pests.

7. The compounds of the probable general formula:

om a-'N=N-N wherein R stands for a benzene nucleus which may be substituted by substituents of the group consisting of alkyl, alkoxy, halogen, the nitro group and a substituted amino group, R stands for an alkyl group which is substituted by a carboxylic acid group, being generally colorless to yellowish colored crystals, being very stable in their dry state and in aqueous and alkaline solution, and being valuable substances in the manufacture of dyestufis and for. combating insect pests.

8. The compounds of the probable general formula:

mula

opO-oom being a yellowish colored crystalline substance, being very stable in its dry state and in aqueous and alkaline solution, and being a valuable substancein the manufacture of dyestufl's and for combating insect pests.

10. Compounds of the probable general formula:

' wherein R stands for the nucleus of an aronyl and cyclohexyl groups which may be sub" stituted by a substituent of the oup consistlng of the COOH, SO H and O..SO2H groups, R sands for a substituent of the group consisting or alkyl, benzyl and cyclohexyl groups substituted by a substituent of the group consisting of the COOH, $0,351 and ObO l-l groups, and the henyl group substituted by a substituent 0 the oup consisting of the SO H and 0.80 groups, and n stands for one of the numbers 1 and 2, being generally colorless to yellowish colored crystals, being very stable in their dry state and in aqueous and alkaline solution, and being valuable substances in the manufacture of dyestuffs and for combating insect pests.

11. Compounds of the probable general formula:

. R-N=N-N/ wherein stands for the nucleus of an aromatic annne capable of producing azo dyestufis whlch may be substituted by substituents of the group consisting of alkyl, alkoxy', I

halogen, the nitro group and a substituted amino group, R stands for a substituent of the group consisting of alkyl, benzyl, phenyl and cyclohexyl groups which may be substituted by a substituent of the roup consisting of the COOH, SO H and .SO H groups, R stands for a substituent of the group cons1st1ng of alkyl, benzyl and cyclohexyl groups substituted by a substituent of the grou con sisting ofthe COOH, SO H and O. 0 H groups, and the phenyl group substituted by a substituent of the group consisting of the SU H and O.SO H groups, being generally colorless to yellowish colored crystals, being very stable in their dry state and in aqueous and alkaline solution, and being valuable substances in the manufacture of dyestuffs and for combating insect pests.

12. Compounds of the probable general formula:

a i am wherein R sfiands' for; a diphenyljl iuele'us which may be substituted by alkox'y. and R and. R fstand fqn .subtitu'ents 'of the group. consistin'gbf elkykbenzyl, phenyl end eylo- 4 hexyl groups yafi l'eest one-cf which contains a; 's'jl lbsfiitunt of the group censisfiing. of the GOQH',-SO,H"end OQSO H groups, being geherelly' colerless'to yellowish colored crys tels,b1eing very stable in their dry state and aqueous and alkeline solution, and being valuable substances in the rrmnufacture of dyestflfl's and for combating insect pests.

I In testimony whereof we have hereunto set our hands.

I w EUGEN GLIETENBERG. L e

WILHELM NEELMEIER; [11.8.] JOSEF HALLER. [n 8.] 

